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Analysis of Microstructural Change Mechanism During High-Temperature Pyrolysis of Carbonaceous Reducing Agents for Silicon Smelting

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Abstract

In this study, X-ray diffraction, Raman spectroscopy, Fourier infrared spectroscopy, and reaction kinetics were used to investigate the microstructure and graphitization mechanism of carbon-reducing agents used in silicon smelting. The results showed that petroleum coke and charcoal exhibited graphitization-like behavior within the temperature range of 1300–1600℃, of which the graphitization degree of petroleum coke was the highest. The correlation analysis revealed that the graphitization degree (g) and the area ratio of D peak to G peak of Raman spectroscopy (R) had a strong correlation coefficient (R2 > 0.9), and the transition temperatures of petroleum coke and charcoal to the graphitization stage were 1720 and 2457℃, respectively. These results showed that petroleum coke was the first to enter the graphitization stage, and the carbon layer structure formed was more stable and orderly, with a higher degree of aromatization. However, due to the high content of alkali metals and the existence of porous structure in charcoal, the reactivity of charcoal was significantly enhanced, thus inhibiting the graphitization reaction. This study provides valuable information for the subsequent research on the mixing ratio of different carbon-reducing agents in silicon smelting.

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References

  1. Kim S-H, Jung J-Y, Wehrspohn RB, Lee J-H (2020) All-room-temperature processed 17.25%-crystalline silicon solar cell. ACS Appl Energy Mater 3(4):3180–3185

    Article  CAS  Google Scholar 

  2. Lu T, Sherman P, Chen X, Chen S, Lu X, McElroy M (2020) India’s potential for integrating solar and on- and offshore wind power into its energy system. Nat Commun 11(1):4750

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  3. Liu C-H, Gu J-C, Yang M-T (2021) A simplified LSTM neural networks for one day-ahead solar power forecasting. IEEE Access 9:17174–17195

    Article  Google Scholar 

  4. Saffar S, Abdullah A, Gouttebroze S, Zhang ZL (2014) Ultrasound-assisted handling force reduction during the solar silicon wafers production. Ultrasonics 54(4):1057–1064

    Article  CAS  PubMed  Google Scholar 

  5. Zhang H, Chen Z, Ma W, Cao S, Jiang K, Zhu Y (2021) The effect of silica and reducing agent on the contents of impurities in silicon produced. Silicon 14(6):2779–2792

    Article  Google Scholar 

  6. Ramírez-Márquez C, Martín-Hernández E, Martín M, Segovia-Hernández JG (2020) Surrogate based optimization of a process of polycrystalline silicon production. Comput Chem Eng 140:106870

    Article  Google Scholar 

  7. Zhu Y, Chen Z, Zhang H, Ma W, Wu J (2022) The effect of Ni on Fe and Al impurities by MIVM model for the silicon production. Energy 254

    Article  CAS  Google Scholar 

  8. Chen Z, Zhou S, Ma W, Deng X, Li S, Ding W (2018) The effect of the carbonaceous materials properties on the energy consumption of silicon production in the submerged arc furnace. J Clean Prod 191:240–247

    Article  CAS  Google Scholar 

  9. Zhang X et al (2023) Porous and graphitic structure optimization of biomass-based carbon materials from 0D to 3D for supercapacitors: a review. Chem Eng J 460:141607

    Article  CAS  Google Scholar 

  10. Zhang H, Chen Z, Ma W, Cao S (2022) Effect of the reactive blend conditions on the thermal properties of waste biomass and soft coal as a reducing agent for silicon production. Renew Energy 187:302–319

    Article  CAS  Google Scholar 

  11. Putman KJ, Rowles MR, Marks NA, de Tomas C, Martin JW, Suarez-Martinez I (2023) Defining graphenic crystallites in disordered carbon: moving beyond the platelet model. Carbon 209:117965

    Article  CAS  Google Scholar 

  12. Wang L, Qiu T, Guo Z, Shen X, Yang J, Wang Y (2021) Changes and migration of coal-derived minerals on the graphitization process of anthracite. ACS Omega 6(1):180–187

    Article  CAS  PubMed  Google Scholar 

  13. Lan C, Tang Y, Huan X, Che Q (2019) Effects of minerals in anthracite on the formation of coal-based graphene. ChemistrySelect 4(19):5937–5944

    Article  CAS  Google Scholar 

  14. Cao H, Li K, Zhang H, Liu Q (2023) Investigation on the mineral catalytic graphitization of anthracite during series high temperature treatment. Minerals 13(6):749

    Article  CAS  Google Scholar 

  15. Destyorini F et al (2021) Formation of nanostructured graphitic carbon from coconut waste via low-temperature catalytic graphitisation. Eng Sci Technol Int J 24(2):514–523

    Google Scholar 

  16. Gomez-Martin A, Schnepp Z, Ramirez-Rico J (2021) Structural evolution in iron-catalyzed graphitization of hard carbons. Chem Mater 33(9):3087–3097

    Article  CAS  Google Scholar 

  17. Li C, Liu X, Zhou Z, Dai Z, Yang J, Wang F (2016) Effect of heat treatment on structure and gasification reactivity of petroleum coke. Int J Coal Sci Technol 3(1):53–61

    Article  CAS  Google Scholar 

  18. Yang J, Xu W, Xu S, Ma S (2022) Study on graphitization of anthracite and petroleum coke catalyzed by boric acid. J Phys Conf Ser 2174(1):012031

    Article  Google Scholar 

  19. Zeng H et al (2022) Insight into the microstructural evolution of anthracite during carbonization-graphitization process from the perspective of materialization. Int J Min Sci Technol 32(6):1397–1406

    Article  CAS  Google Scholar 

  20. Liang D, Xie Q, Wan C, Li G, Cao J (2019) Evolution of structural and surface chemistry during pyrolysis of Zhundong coal in an entrained-flow bed reactor. J Anal Appl Pyrol 140:331–338

    Article  CAS  Google Scholar 

  21. Xia S et al (2021) Reaction kinetics, mechanism, and product analysis of the iron catalytic graphitization of cellulose. J Clean Prod 329:129735

    Article  CAS  Google Scholar 

  22. Zhou H, Wu C, Pan J, Wang Z, Niu Q, Du M (2021) Research on molecular structure characteristics of vitrinite and inertinite from bituminous coal with FTIR, micro-raman, and XRD spectroscopy. Energy Fuels 35(2):1322–1335

    Article  CAS  Google Scholar 

  23. Zou L, Huang B, Huang Y, Huang Q, Ca W (2003) An investigation of heterogeneity of the degree of graphitization in carbon–carbon composites. Mater Chem Phys 82(3):654–662

    Article  CAS  Google Scholar 

  24. Käärik M, Arulepp M, Karelson M, Leis J (2008) The effect of graphitization catalyst on the structure and porosity of SiC derived carbons. Carbon 46(12):1579–1587

    Article  Google Scholar 

  25. Biscoe J, Warren BE (1942) An X-ray study of carbon black. J Appl Phys 13(6):364–371

    Article  CAS  Google Scholar 

  26. Luz AP, Renda CG, Lucas AA, Bertholdo R, Aneziris CG, Pandolfelli VC (2017) Graphitization of phenolic resins for carbon-based refractories. Ceram Int 43(11):8171–8182

    Article  CAS  Google Scholar 

  27. Jorio A, Saito R (2021) Raman spectroscopy for carbon nanotube applications. J Appl Phys 129(2):021102

    Article  CAS  Google Scholar 

  28. Li Z, Deng L, Kinloch IA, Young RJ (2023) Raman spectroscopy of carbon materials and their composites: Graphene, nanotubes and fibres. Prog Mater Sci 135:101089

    Article  CAS  Google Scholar 

  29. Made Joni I, Vanitha M, Camellia P, Balasubramanian N (2018) Augmentation of graphite purity from mineral resources and enhancing % graphitization using microwave irradiation: XRD and Raman studies. Diam Relat Mater 88:129–136

    Article  Google Scholar 

  30. Meng D, Yue C, Wang T, Chen X (2021) Evolution of carbon structure and functional group during Shenmu lump coal pyrolysis. Fuel 287:119538

    Article  CAS  Google Scholar 

  31. Wang Y, Liang L, Zhu B, Tian Y, Li G (2022) Economical preparation of Fe3O4/C/CG and Fe/C/CG composites as microwave absorbents by recycling of coal gangue. Mater Res Bull 146:111573

    Article  CAS  Google Scholar 

  32. Wang P et al (2020) Ultraviolet Raman spectra: The reasonable method of evaluating coal pyrolysis graphitization. AIP Adv 10(11):115007

    Article  CAS  Google Scholar 

  33. Zhang X, Li H, Zhang K, Wang Q, Qin B, Cao Q, Le J (2018) Strategy for preparing porous graphitic carbon for supercapacitor: balance on porous structure and graphitization degree. J Electrochem Soc 165(10):A2084–A2092

    Article  CAS  Google Scholar 

  34. Cao M et al (2022) Coupling Fe(3) C nanoparticles and N-doping on wood-derived carbon to construct reversible cathode for Zn-air batteries. Small 18(26):e2202014

    Article  PubMed  Google Scholar 

  35. Gao F, Liang L, Mao L, Wang Y, Zhu B, Zhang R, Li G (2022) Achievement of excellent microwave absorption on the Co/C-based composite from coal hydrogasification residue. Diam Relat Mater 129:109374

    Article  CAS  Google Scholar 

  36. Pejcic B, Heath C, Pagès A, Normore L (2021) Analysis of carbonaceous materials in shales using mid-infrared spectroscopy. Vib Spectrosc 112:103186

    Article  CAS  Google Scholar 

  37. Amemiya T, Okada S, Kagami H, Nishiyama N, Yao Y, Sakoda K, Hu X (2022) High-speed infrared photonic band microscope using hyperspectral fourier image spectroscopy. Opt Lett 47(10):2430–2433

    Article  PubMed  Google Scholar 

  38. Russo C, Stanzione F, Tregrossi A, Ciajolo A (2014) Infrared spectroscopy of some carbon-based materials relevant in combustion: qualitative and quantitative analysis of hydrogen. Carbon 74:127–138

    Article  CAS  Google Scholar 

  39. Xie X, Liu L, Lin D, Zhao Y, Qiu P (2019) Influence of different state alkali and alkaline earth metal on chemical structure of Zhundong coal char pyrolyzed at elevated pressures. Fuel 254:115691

    Article  CAS  Google Scholar 

  40. Veloso VA, Silva DL, Gastelois PL, Furtado CA, Santos AP (2022) Polyaniline/graphene nanocomposite: effect of the graphene functionalization with a long-chain fatty acid. Mater Chem Phys 285:126162

    Article  CAS  Google Scholar 

  41. Qiu T, Yang J-g, Bai X-j (2020) Insight into the change in carbon structure and thermodynamics during anthracite transformation into graphite. Int J Miner Metall Mater 27(2):162–172

    Article  CAS  Google Scholar 

  42. Mehta N, Kumar A (2016) Some new observations on activation energy of crystal growth for thermally activated crystallization. J Phys Chem B 120(6):1175–1182

    Article  CAS  PubMed  Google Scholar 

  43. Zhang S, Liu Q, Zhang H, Ma R, Li K, Wu Y, Teppen BJ (2020) Structural order evaluation and structural evolution of coal derived natural graphite during graphitization. Carbon 157:714–723

    Article  CAS  Google Scholar 

  44. Huang J-X, Csányi G, Zhao J-B, Cheng J, Deringer VL (2019) First-principles study of alkali-metal intercalation in disordered carbon anode materials. J Mater Chem A 7(32):19070–19080

    Article  CAS  Google Scholar 

  45. Speyer L, Fontana S, Cahen S, Hérold C (2020) Intercalation of sodium and heavy alkali metals into graphenic foams. Microporous Mesoporous Mater 306:110344

    Article  CAS  Google Scholar 

  46. Lin X, Huang J, Zhang B (2019) Correlation between the microstructure of carbon materials and their potassium ion storage performance. Carbon 143:138–146

    Article  CAS  Google Scholar 

  47. Destyorini F, Yudianti R, Irmawati Y, Hardiansyah A, Hsu Y-I, Uyama H (2021) Temperature driven structural transition in the nickel-based catalytic graphitization of coconut coir. Diam Relat Mater 117:108443

    Article  CAS  Google Scholar 

  48. Kabir Ahmad R, Anwar Sulaiman S, Yusup S, Sham Dol S, Inayat M, Aminu Umar H (2022) Exploring the potential of coconut shell biomass for charcoal production. Ain Shams Eng J 13(1):101499

    Article  Google Scholar 

Download references

Acknowledgements

The authors are grateful for financial support from the Major Projects of Yunnan Province (No. 202102AB080013 and No. 202303AC100006) and the Key Science and Technology Specific Projects of Yunnan Province (N0.202202AG050012) and the Ten Thousand Talent Plans for Young Top-notch Talents of Yunnan Province (No. YNWR-QNBJ-2020-022).

Funding

The authors are grateful for financial support from the Major Projects of Yunnan Province (No. 202102AB080013 and No. 202303AC100006) and the Key Science and Technology Specific Projects of Yunnan Province (N0.202202AG050012) and the Ten Thousand Talent Plans for Young Top-notch Talents of Yunnan Province (No. YNWR-QNBJ-2020–022).

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Authors and Affiliations

  1. Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, 650093, China

    Chenggang Tao, Zhengjie Chen & Wenhui Ma

  2. State Key Laboratory of Complex Nonferrous Metal Resources Cleaning Utilization in Yunnan Province, Kunming University of Science and Technology, Kunming, 650093, China

    Chenggang Tao, Zhengjie Chen & Wenhui Ma

  3. The National Engineering Laboratory for Vacuum Metallurgy, Kunming University of Science and Technology, Kunming, 650093, China

    Zhengjie Chen & Wenhui Ma

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  1. Chenggang Tao
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Contributions

Chenggang Tao: Conceptualization, Resources, Writing—review & editing, Visualization, Validation, Supervision. Zhengjie Chen: Conceptualization, Methodology, Validation, Formal analysis, Investigation, Data curation; Wenhui Ma: Formal analysis, Validation, Data curation.

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Correspondence to Zhengjie Chen.

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Tao, C., Chen, Z. & Ma, W. Analysis of Microstructural Change Mechanism During High-Temperature Pyrolysis of Carbonaceous Reducing Agents for Silicon Smelting. Silicon 16, 647–663 (2024). https://doi.org/10.1007/s12633-023-02701-2

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